CN102336856B - Special effect boron adsorption resin and synthetic method and application thereof - Google Patents
Special effect boron adsorption resin and synthetic method and application thereof Download PDFInfo
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- CN102336856B CN102336856B CN201110185413.8A CN201110185413A CN102336856B CN 102336856 B CN102336856 B CN 102336856B CN 201110185413 A CN201110185413 A CN 201110185413A CN 102336856 B CN102336856 B CN 102336856B
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- diethyl malonate
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Abstract
The invention relates to a special effect boron adsorption resin and a synthetic method and application thereof, belonging to the fields of high molecules and waste water treatment. The general structural formula of the resin is shown in the specifications, wherein n=1,000-2,000. The method comprises the following steps of: (1) preparing 2-amino-1,3-propylene glycol; (2) preparing chloromethylated styrene-divinylbenzene copolymerized spheres; and (3) preparing the special effect boron adsorption resin from the 2-amino-1,3-propylene glycol and the chloromethylated styrene-divinylbenzene copolymerized spheres. The special effect boron adsorption resin can be used for extracting and recovering boric acid from an acid aqueous solution. In the invention, the special effect boron adsorption resin which is suitable for a strongly acid environment is synthesized by taking 1,3-propylene glycol as a functional group.
Description
Technical field
The present invention relates to a kind of synthetic and application of boron polymeric adsorbent, belong to polymer and field of waste water treatment.
background of invention
Boron is very wide in industrial application, and the separation of water mesoboric acid is removed and had very important significance.General anionite-exchange resin can adsorb boric acid from the aqueous solution.But to the selectivity of boric acid, not fine, and poor to the adsorptive power of boric acid when in water, electrolyte concentration is high, therefore take polyhydroxylated thing as basic boron-selective resins, be developed, boron-selective resins the earliest comes across nineteen fifty-seven.Lyman and Preuss make a kind of resin with oxygen polystyrene and the N-methyl glucoside amine reaction that methylates.Its reaction formula is as follows:
What this resin synthesized at first is gel-type, has then synthesized macroporous ion-exchange resin.D564 is the domestic resin that boron is had to special efficacy absorption property the earliest, can only in neutrality or alkaline medium, use.Developed again subsequently D201, D403 type macroporous anion exchange resin, XSC-700 resin etc., these resins all take with N-methyl glucoside amine as function base, can only in slightly acidic, neutrality and alkaline medium, use.This is because H is all emitted in the type resin and boric acid complexing
+, form boric acid-polyhydric alcohol complex thing of 1:1, more further react generation 1:2 complex compound.The people such as He Ping Lin have carried out systematic research to poly-hydroxy functional resin and boric acid with reacting of polyol.
Japanese Patent JP2002226517 has introduced a kind of synthetic method of heterogeneous resin, this resin is take cross-linked styrene polymerization methyl propenoic acid glycidyl fat as resin matrix N-methyl glucoside amine is as function base, borate ion is had to very high exchange capacity, can be used for waste water reclamation, seawater or drink water purification.Michael Schelhaas, Koln(DE) invented a kind of monodisperse macroporous boric acid selective resin, this resin take vinylbenzene-divinylbenzene as resin matrix, N-methyl glucoside amine is the synthetic weak base anion-exchange resin of function base, resin than JP2002226517 invention is good to the adsorption effect of boron, but still is only applicable to the absorption of boron in neutral and weak acidic medium.The people such as Chinese Academy of Sciences's Lina WANG use methyl glucoside amine (MG) by the macroporous copolymer functional modification of glycidyl methacrylate (GMA) and trimethylammonium vinylformic acid three methanol-based propane esters (TRIM), prepare novel boron special efficacy resin, compared with traditional boron special efficacy polymeric adsorbent, adsorptive capacity is obviously larger, and in pH value, be that 2 left and right still have absorption to boric acid, adsorptive capacity is about 0.5mmol/g.
Due in many waste water containing borons acid dense, as contained 20% the vitriol oil in Isosorbide-5-Nitrae-dihydroxyanthraquinone waste water, be strongly-acid system, therefore above-mentioned resin is not all suitable for the recovery of Boron in Wastewater acid.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, provide a kind of boron polymeric adsorbent, synthetic method and application.
It is skeleton that the present invention adopts vinylbenzene-divinylbenzene copolymerization spheroid, by chloromethylation and amination, introduces secondary amine group:
Its basic synthetic route is:
A kind of boron polymeric adsorbent of the present invention, its general structure is:
Wherein n=1000 ~ 2000.
The preparation method of a kind of boron polymeric adsorbent of the present invention, carries out in accordance with the following steps:
(1) preparation of 2-amino-1,3-propanediol: take diethyl malonate, Sodium Nitrite, Glacial acetic acid as raw material, water is solvent, reacts at normal temperatures 24h and obtains the different diethyl malonate of nitrosylation intermediate product; The back flow reaction 5h reduction in ethanolic soln of different diethyl malonate and sodium Metal 99.5 obtains 2-amino-1,3-propanediol; Wherein mole proportioning of diethyl malonate, Sodium Nitrite, Glacial acetic acid is 1:3:3, and the mol ratio of different diethyl malonate and sodium Metal 99.5 is 1:10 ~ 20.
(2) press 2-amino-1, the ratio of mol ratio 1:2 ~ 10 of ammediol and chloromethylation vinylbenzene-divinylbenzene copolymerization spheroid cl content, vinylbenzene-divinylbenzene copolymerization spheroid that will methylate is first used solvent pre-treatment, make resin Archon fully swelling, and then 2-amino-1,3-propanediol is joined in reaction flask, react to the pH value stopped reaction that no longer raises, filter, obtain boron polymeric adsorbent.
Wherein the solvent described in step (2) is methylene dichloride, DMF, ethylene dichloride etc.
The application of a kind of boron polymeric adsorbent of the present invention, it can be used for extraction and the recovery of acidic aqueous solution mesoboric acid.
Superiority of the present invention is:
Document < < boric acid and polyol react and boron-selective resins > > in Review Study the Complexing mechanism of multiple polyol and boric acid, wherein polyvalent alcohol, fat cyclic polyols, carbohydrate, dihydric phenols, hydroxyl acids etc. and boric acid complexing, there is proton hydrogen to emit, make the adsorptive capacity of resin in strong acidic environment very low.But there is following complex reaction in 1,3-PD and boric acid:
This reaction, boric acid and a glycol complexing form six-ring, do not emit proton hydrogen.Therefore, will be take 1,3-PD as function base, the synthetic boric acid polymeric adsorbent that is applicable to strong acidic environment.
Embodiment
Below example is further set forth preparation method of the present invention by experiment, but this should be interpreted as to the scope of theme of the present invention only limits to following embodiment.
Example 1
Step 1: the preparation of 2-amino-1,3-propanediol
In 250mL four-hole boiling flask, add 32.04g(0.2mol) diethyl malonate and 40ml Glacial acetic acid, after stirring at room 10min, be cooled to-5 ℃, between-10 ℃-0 ℃, drip 41.4g(0.6mol) solution of Sodium Nitrite and 60mL water composition, dropwise, be warming up to 30 ℃, stir 24h.With dichloromethane extraction product isonitroso diethyl malonate, more successively with saturated sodium carbonate solution, saturated aqueous common salt and water washing, anhydrous sodium sulfate drying, suction filtration, solvent evaporated obtains isonitroso diethyl malonate 36.32g.
In 1000mL four-hole boiling flask, add 18.92g(0.1mol) isonitroso diethyl malonate, 500mL dehydrated alcohol, 45 ℃-50 ℃ of temperature controls add sodium Metal 99.5 34.49g(1.5mol), finish, be heated to back flow reaction 6h, react complete and to be cooledly add 150mL water to room temperature, stir 10min, temperature control is below 35 ℃, with 35% concentrated hydrochloric acid adjust pH to 3, use again sodium hydroxide adjust pH to 8-9, stop stirring, filter, to after filtrate decompression (52 ℃) evaporate to dryness, add absolute dehydrated alcohol 50ml, gac 2g, stir 30min, filter to obtain 2-amino-1, the ethanolic soln 48mL of ammediol (about 0.08mol).
The structural formula of gained 2-amino-1,3-propanediol is:
Step 2: resin chlorine ball amination
The styrene-divinyl benzene resin 2g that gets degree of crosslinking and be 10 chloromethylation, cl content is 13% dry dose, after DMF is fully swelling, filters, and with ethanol rinsing twice, joins in 50mL there-necked flask, adds step 1 filtrate 22mL, 50 ℃ of temperature controls, reaction 5h.React complete, filter to obtain aminated resin, the content of resin functional group is 27.4% dry dose.Through infrared measurement, gained resin is at γ=3389cm
-1there are stronger amino absorption peak, CH in place
2c-Cl stretching vibration peak γ=674cm in Cl
-1with 4 by CH
2cl replaces in-plane bending vibration peak γ=1265cm of the Isosorbide-5-Nitrae-disubstituted benzenes=C-H of strengthening
-1disappear.Its structural formula is as follows:
Wherein n=1000 ~ 2000.
Example 2
Step 1: the preparation of 2-amino-1,3-propanediol
With example 1 step 1.
Step 2: resin chlorine ball amination
The styrene-divinyl benzene resin 2g that gets degree of crosslinking and be 6 chloromethylation, cl content is 20% dry dose, after DMF is fully swelling, filters, and with ethanol rinsing twice, joins in 100mL there-necked flask, adds step 1 filtrate 34mL, 80 ℃ of temperature controls, reaction 5h.React complete, filter to obtain aminated resin, dry dose of the content 38.8% of resin functional group.Through infrared measurement, gained resin is at γ=3389cm
-1there are stronger amino absorption peak, CH in place
2c-Cl stretching vibration peak γ=674cm in Cl
-1with 4 by CH
2cl replaces in-plane bending vibration peak γ=1265cm of the Isosorbide-5-Nitrae-disubstituted benzenes=C-H of strengthening
-1disappear.Its structural formula is with embodiment 1.
Example 3
Step 1: the preparation of 2-amino-1,3-propanediol
With example 1 step 1.
Step 2: resin chlorine ball amination
The styrene-divinyl benzene resin 2g that gets degree of crosslinking and be 10 chloromethylation, cl content is 17.8% dry dose, through 1, the fully swelling rear filtration of 2-ethylene dichloride, with ethanol rinsing twice, joins in 50mL there-necked flask, add step 1 filtrate 30mL, 70 ℃ of temperature controls, reaction 5h.React complete, filter to obtain aminated resin, the content of resin functional group is 35.5% dry dose.Through infrared measurement, gained resin is at γ=3389cm
-1there are stronger amino absorption peak, CH in place
2c-Cl stretching vibration peak γ=674cm in Cl
-1with 4 by CH
2cl replaces in-plane bending vibration peak γ=1265cm of the Isosorbide-5-Nitrae-disubstituted benzenes=C-H of strengthening
-1disappear.Its structural formula is with embodiment 1.
Example 4
Step 1: the preparation of 2-amino-1,3-propanediol
With example 1 step 1.
Step 2: resin chlorine ball amination
The styrene-divinyl benzene resin 2g that gets degree of crosslinking and be 8 chloromethylation, cl content is 18.8% dry dose, through 1, the fully swelling rear filtration of 2-ethylene dichloride, with ethanol rinsing twice, joins in 50mL there-necked flask, add step 1 filtrate 32mL, 80 ℃ of temperature controls, reaction 5h.React complete, filter to obtain aminated resin, the content of resin functional group is 37.0% dry dose.Through infrared measurement, gained resin is at γ=3389cm
-1there are stronger amino absorption peak, CH in place
2c-Cl stretching vibration peak γ=674cm in Cl
-1with 4 by CH
2cl replaces in-plane bending vibration peak γ=1265cm of the Isosorbide-5-Nitrae-disubstituted benzenes=C-H of strengthening
-1disappear.Its structural formula is with embodiment 1.
Example 5
Step 1: the preparation of 2-amino-1,3-propanediol
With example 1 step 1.
Step 2: resin chlorine ball amination
The styrene-divinyl benzene resin 2g that gets degree of crosslinking and be 7 chloromethylation, cl content is 15% dry dose, through 1, the fully swelling rear filtration of 2-ethylene dichloride, with ethanol rinsing twice, joins in 50mL there-necked flask, add step 1 filtrate 5mL, dehydrated alcohol 15mL, normal-temperature reaction 24h.React complete, filter to obtain aminated resin, the content of resin functional group is 30.9% dry dose.Through infrared measurement, gained resin is at γ=3389cm
-1there are stronger amino absorption peak, CH in place
2c-Cl stretching vibration peak γ=674cm in Cl
-1with 4 by CH
2cl replaces in-plane bending vibration peak γ=1265cm of the Isosorbide-5-Nitrae-disubstituted benzenes=C-H of strengthening
-1disappear.Its structural formula is with embodiment 1.
Example 6
Step 1: the preparation of 2-amino-1,3-propanediol
With example 1 step 1.
Step 2: resin chlorine ball amination
The styrene-divinyl benzene resin 2g that gets degree of crosslinking and be 4 chloromethylation, cl content is 22%, through 1, the fully swelling rear filtration of 2-ethylene dichloride, with ethanol rinsing twice, joins in 50mL there-necked flask, add step 1 filtrate 13mL, dehydrated alcohol 7mL, 40 ℃ of reaction 6h of temperature control.React complete, filter to obtain aminated resin, the content of resin functional group is 41.7% dry dose.Through infrared measurement, gained resin is at γ=3389cm
-1there are stronger amino absorption peak, CH in place
2c-Cl stretching vibration peak γ=674cm in Cl
-1with 4 by CH
2cl replaces in-plane bending vibration peak γ=1265cm of the Isosorbide-5-Nitrae-disubstituted benzenes=C-H of strengthening
-1obviously weaken.Its structural formula is with embodiment 1.
7 one kinds of boron polymeric adsorbents of example are for the extraction and recovery example of acidic aqueous solution mesoboric acid
Washing three times repeatedly refluxes the resin making in example 1 ~ 6 in Soxhlet extractor, to remove the unnecessary organism containing in resin, again with certain density sulphuric acid soln washing, with deionized water, be washed till neutrality afterwards, with certain density sodium hydroxide solution washing, finally extremely neutral with deionized water wash again, upper prop, by sulfuric acid concentration, be the waste water of 20% boronic acid containing 2% left and right with certain flow rate through resin bed, to the resin absorption that reaches capacity.By the resin of the adsorptive capacity that reaches capacity deionized water wash-out, concentrated recrystallization obtains boric acid.
After absorption, the structural formula of resin is:
。
Claims (2)
1. a preparation method for boron polymeric adsorbent, its general structure is:
Wherein n=1000 ~ 2000, is characterized in that carrying out in accordance with the following steps:
(1) preparation of 2-amino-1,3-propanediol: take diethyl malonate, Sodium Nitrite, Glacial acetic acid as raw material, water is solvent, reacts at normal temperatures 24h and obtains nitrosylation intermediate product isonitroso diethyl malonate; The back flow reaction 5h reduction in ethanolic soln of isonitroso diethyl malonate and sodium Metal 99.5 obtains 2-amino-1,3-propanediol; Wherein mole proportioning of diethyl malonate, Sodium Nitrite, Glacial acetic acid is 1:3:3, and the mol ratio of isonitroso diethyl malonate and sodium Metal 99.5 is 1:10 ~ 20;
(2) press 2-amino-1, the ratio of mol ratio 1:2 ~ 10 of ammediol and chloromethylation vinylbenzene-divinylbenzene copolymerization spheroid cl content, chloromethylation vinylbenzene-divinylbenzene copolymerization spheroid is first used to solvent pre-treatment, make resin Archon fully swelling, and then 2-amino-1,3-propanediol is joined in reaction flask, react to the pH value stopped reaction that no longer raises, filter, obtain boron polymeric adsorbent.
2. the preparation method of a kind of boron polymeric adsorbent according to claim 1, is characterized in that wherein the solvent described in (2) is methylene dichloride, DMF, ethylene dichloride.
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| CN103803676A (en) * | 2013-12-30 | 2014-05-21 | 中国神华能源股份有限公司 | Method for removing arsenic in water |
| CN105016502B (en) * | 2014-04-29 | 2017-09-08 | 中国石油化工集团公司 | A kind of geothermal tail water removes boron device and processing method |
| CN104445781B (en) * | 2014-11-27 | 2016-03-23 | 浙江奇彩环境科技股份有限公司 | A kind of administering method of fused ring compound waste water |
| CN105753819B (en) * | 2016-04-26 | 2018-06-08 | 张玲 | A kind of method of 5 hydroxymethyl furfural purifying |
| CN105884721B (en) * | 2016-04-26 | 2017-11-24 | 张玲 | A kind of method of 2,5 furans dicarbaldehyde purifying |
| CN106629975A (en) * | 2016-12-27 | 2017-05-10 | 南京慧城水处理设备有限公司 | Method used for removing trace boron in desalination seawater with boron selective chelating resin |
| CN108554391A (en) * | 2017-12-08 | 2018-09-21 | 孝感市锐思新材科技有限公司 | One kind three（Trimethyl silane）The preparation method of borate polymeric material |
| CN111039381A (en) * | 2018-10-15 | 2020-04-21 | 中国科学院过程工程研究所 | Method for improving quality of reverse osmosis seawater desalination produced water |
| CN112321837B (en) * | 2020-10-19 | 2022-04-29 | 江苏威奇达药业有限公司 | Resin for adsorbing boric acid in azithromycin process and preparation method thereof |
| CN115155529A (en) * | 2021-04-01 | 2022-10-11 | 南开大学 | Boron adsorption resin and preparation method thereof |
| CN114682229B (en) * | 2022-03-29 | 2023-04-25 | 西安蓝深新材料科技股份有限公司 | Boron adsorption resin and preparation method and application thereof |
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